Stabilized diazo guanylurea



Patented Oct. 20, 1942 STABILIZED DIAZO GUANYLUREA COMPOUNDS Paul P.McClellan, Old Greenwich, and Walter P. Ericks, Cos Cob, Conn.,assignors to American Cyanamid Company, New York, N. Y., a corporationof Maine No Drawing. Original application December 12,

1940, Serial N0. 369,806. Divided and this application August 30, 1941,Serial No. 409,060

3 Claims. .(Cl. 260140) This invention relates to a new class ofchemical compounds, to intermediates and dyes obtained therefrom, and totheir methods of preparation.

The principal object of this invention is to prepare new stabilizeddiazo compounds, preferably those soluble in water and in the morecommonly used organic solvents.

Among the stabilized diazo compounds included herein are, moreespecially, the reaction products of an ice color diazo component withan alkylol or an alkoxyalkylol derivative or guanylurea. Inasmuch asthese derivatives each exist in several tautomeric forms, the reactionproducts prepared from any one may occur as a mixture of isomers whichreadily undergo rearrangement. Hence, assignment of a definite chemicalformula is problematical.

However, the chemical properties of the products and the particularmethod or methods of preparation disclosed herein cause one of theisomers to appear in excess, and under the present conditions themonomeric form is produced predominantly. Thus the alkylol andalkoxyalkylol guanylurea derivatives probably give:

in which R represents the nucleus of an aromatic amine such as thenucleus of an ice color diazo component; and R2 is an alkylol oralkoxyalkylol group.

These stabilized diazo compounds are resistant to percussion and evenwhen heated in a direct flame decompose without the hazard of anexplosion. When in a dry condition or in an alkaline solution they arestable at temperatures normally encountered throughout all seasons ofthe year, and hence may be stored indefinitely. However, these reactionproducts possess the property of splitting into their originalcomponents by treatment with acids at elevated temperatures or withsteam containing volatile acid vapors. If this splitting occurs in thepresence of an ice color coupling component the regenerated activediazotized component becomes available immediately for reaction with thecoupling component and produces the corresponding azo pigment or dye.

To this end it is a further object of this invention to prepare new azopigments and dyes by mixing an ice color coupling component and thereaction product of an ice color diazo component guanylurea. As such,the mixture may or may not be colored. However, if a textile material isprinted or impregnated with this mixture and then heated in the presenceof an acid, the acid hydrolyzes the stable diazo compound, splitting itinto its components; and the regenerated diazotized component liberatedcouples with the ice color coupling component to form an azo pigment ordye.

This acid treatment or ageing as it is called, is preferably efiectedwith a weak acid and at an elevated temperature. Usually formic oracetic acids are used, but various other acids as well as substancesliberating acids upon being steamed such as ammonium sulfate, esters oftartaric, succinic, etc., acids may be used particularly when theprinted material is subjected to'a subsequent steam treatment to effectageing or develop the color.

Stable alkaline printing pastes can be prepared from the mixture of theice color coupling component and the reaction product of the ice colordiazo component with one of the alkylol or alkoxyalkylol derivatives bydissolving the mixture in a solvent such as water, alcohol, acetone,etc., together with various other ingredients such as alkalies, organicbases, impregnating agents, thickeners such as starch, gum, etc., wellknown to those skilled in the art. Cotton goods can be printed with thispaste with the aid of a copper roll. The print is then dried andsubsequently the desired color is developed by steaming in the presenceof acetic acid or other volatile acid vapors. In this manner aninsoluble azo pigment is produced in and on the cotton fibers in theform of the printed pattern. Such prints are bright and possessremarkable fastness to light and washing.

The facility with which the compounds and dyes included in thisinvention can be used is based upon the ease with which the. stabilizeddiazamino group present can be split and converted into an active diazogroup by heating in the presence of an acid or an acid liberatingsubstance. This conversion or ageing is usually effected in a steamchamber and in the presence of a coupling component. Under theseconditions the active diazo group is free for such a short time intervalthat it does not decompose and instead couples with the couplingcomponent (e. g. naphthol in the example given below) to develop or formthe color.

The following example describes the preparation of several stabilizeddiazo compounds inwith an alkylol or alkoxyalkylol derivative of cludedin this invention and further gives details as to their use in dyeingand printing textile materials.

EXAMPLE I Ethylol gua ylurea reacted with p-toluidz'ne diazom'umhydrochloride An aqueous solution of ethylol guanylurea was prepared byreacting 33.8 g. of guanylurea sul- This mixture was constantly stirredfor 3 hours at about 10 C. with 8.8 g. of ethylene oxide. It was thenreacted for an additional 3 hours While cooled and stirred and thenfurther cooled to C.

23.1 g. of p-toluidine' diazonium chloride was and was filtered off anddried at room temperature.

This diazo compound has the following probable formula:

It is almost insoluble in water but soluble in denatured ethyl alcoholand acetone.

Any one of a number of coupling components known to those versed in theart can be admixed with this diazo compound, such as l-naphthol, theo-toluidide of 2,3-hydroxy-naphthoic acid, the 2,5-dimethoxy anilide of2,3-hydroxy-naphthoic acid, or the 4-chlorani1ide of2,3-hydroxynaphthoi-c acid. 7 When mixed with an alkaline solution ofsodium wnaphtholate it was stable but the formation of a red azodyestufi upon addition of acetic acid and heating the mixture showedthat coupling was readily efiected in an acid medium at an elevatedtemperature.

Similarly, various other members of the alkylol and alkoxyalkylol seriesof derivatives of 1 fate in water and at 23 0'. with 11.2 g. of cal--1 3cium hydroxide slurred in 50 cc. of water.

added to the above ethylol guanylurea solution with stirring. A brownpowder precipitated out guanylurea may be obtained by using as astartthe stabilized diazo compound water soluble. A

number of such compounds are described in the co-pending applicationsSerial Numbers 289,398

and 289,400 of Walter P. Ericks.

It is to be particularly noted that although for ease of description thearomatic amine chosen in the example illustrating specific embodimentsof the invention was p-toluidine, various other stable diazo compoundscan be prepared from practically anyice color diazo component. Thusother typical amines which can i be. diazotized and reacted with thestabilizing components include in addition to p-toluidine, amongnumerous others familiar to those versed in the art, aniline as Well ashomologues of aniline, namely 2,4-dimethylaniline. Where still othercolor variations are desired, the halogen derivatives of aniline may beused, such as the monochloroanilines, dichloranilines; anilinessubstituted by hydrocarbon radicals, such as alkyl, alkoxy radicals, forexample methyl, ethyl,

etc., methoxy, ethoxy, or the like; or anilines substituted by nitroradicals, acyl derivatives thereof, and the like.

Similarly, although l-naphthol is given as the most frequently usedcoupling component for the dye mixture incorporating the specificstabilized diazo compounds, various other naphthols, such as naphtholAS, toluidides, pyrazolones, coupling arylides, particularly arylides of2,3- hydroxy-naphthoic acid, other hydroxy or amino-naphthoic acids,carbazole-carboxylic acid, 'hydroxy-anthracene carboxylic acid, an.-thraquinone carboxylic acid, the anilide of 2,3- hydroxy-naphthoic acid,or the like, may be used as coupling components.

This case is a division of our co-pending application, Serial No.369,806, filed Dec. l2, 1940.

It is to be understood that the examples herein given are merelyillustrative and not, limitative embodiments of this invention which isto be construed broadly and limited solely as defined by the scope ofthe appended claims.

We claim:

1. A stabilized diazo general formula:

in which R is the nucleus of an ice color diazo in which R is thenucleus of an ice color diazo component of the benzene series and X is asaturated aliphatic radical having at least two carbon atoms.

3. A stabilized diazo compound having the formula:

I R-N=N-N-lCNHfll-l lcHiCHzOH in which R is the nucleus of an ice/colordiazo component of the benzene series.

PAUL P. MCCLELLAN. WALTER P. ERICKS.

